title: Highly diastereoselective arylations of substituted piperidines.
abstract: A highly diastereoselective methodology for the preparation of various substituted piperidines via Negishi cross-couplings with (hetero)aryl iodides was developed. Depending on the position of the C-Zn bond relative to the nitrogen (position 2 vs position 4), the stereoselectivity of the coupling can be directed toward either the trans- or cis-2,4-disubstituted products. Density functional theory calculations on the relative stabilities of the Zn and Pd intermediates were performed to explain the high diastereoselectivities obtained. A novel 1,2-migration of Pd further expands this method to the stereoselective preparation of 5-aryl-2,5-disubstituted piperidines.
authors.affiliation: Department Chemie, Ludwig-Maximilians-Universität München, Butenandtstr. 5-13, Haus F, 81377 Munich, Germany.
authors.forename: Stephanie
authors.initials: S
authors.lastname: Seel
authors.forename: Tobias
authors.initials: T
authors.lastname: Thaler
authors.forename: Keishi
authors.initials: K
authors.lastname: Takatsu
authors.forename: Cong
authors.initials: C
authors.lastname: Zhang
authors.forename: Hendrik
authors.initials: H
authors.lastname: Zipse
authors.forename: Bernd F
authors.initials: BF
authors.lastname: Straub
authors.forename: Peter
authors.initials: P
authors.lastname: Mayer
authors.forename: Paul
authors.initials: P
authors.lastname: Knochel
mesh_terms: D015394:Molecular Structure; D010880:Piperidines / Q000138:chemical synthesis* / Q000737:chemistry; D011789:Quantum Theory; D013237:Stereoisomerism
chemical_list: D010880:Piperidines